EP0150256A2 - Method for producing crystalline ZSM-5- or ZSM-11-zeolites - Google Patents

Method for producing crystalline ZSM-5- or ZSM-11-zeolites Download PDF

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EP0150256A2
EP0150256A2 EP84108958A EP84108958A EP0150256A2 EP 0150256 A2 EP0150256 A2 EP 0150256A2 EP 84108958 A EP84108958 A EP 84108958A EP 84108958 A EP84108958 A EP 84108958A EP 0150256 A2 EP0150256 A2 EP 0150256A2
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sio
aged
crystallization
nucleation gel
gel
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EP0150256B1 (en
EP0150256A3 (en
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Hartmut Dr. Dipl.-Chem. Kacirek
Andreas Dipl.-Chem. Meyer
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Sued Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2876—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures from a reacting mixture containing an amine or an organic cation, e.g. a quaternary onium cation-ammonium, phosphonium, stibonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
    • C01B33/185—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process of crystalline silica-polymorphs having molecular sieve properties, e.g. silicalites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241

Definitions

  • the invention relates to a method for producing crystalline zeolitic aluminosilicates, in particular of the ZSM-5 or ZSM-11 structure type.
  • the Si / A1 atomic ratio is generally * 10, and in extreme cases the aluminum content can go to zero.
  • the "aluminosilicates" without aluminum or with a low aluminum content are referred to as "silicalites”.
  • the crystalline zeolitic aluminosilicates of the structure types ZSM-5 or ZSM-11 are becoming increasingly important as catalysts and catalyst supports.
  • Zeolithic aluminosilicates of the structure type ZSM-5 can be produced, for example, according to US Pat. No. 3,702,866 from mixtures of reactive Si0 2 and A1 2 0 3 by hydrothermal crystallization in the presence of sodium ions and quaternary ammonium compounds, such as tetrapropylammonium salts.
  • a disadvantage of this and similar processes is that the crystallization times are very long at economically interesting concentrations of the tetrapropylammonium ion.
  • ZSM-5 crystals of different sizes are formed in these processes, which is disadvantageous for use as catalysts.
  • the object of the invention is to provide a process for the production of crystalline zeolitic aluminosilicates which is free from the disadvantages of the prior art.
  • the rate of hydrothermal crystallization should be increased considerably and at the same time the crystal size of the end product, which is in the range from 0.1 to 100 ⁇ m, should be influenced.
  • the invention thus relates to a process for the production of crystalline zeolitic aluminosilicates with a Si / Al atomic ratio of * 10 by hydrothermal crystallization from a reaction mixture which contains Si0 2 and Al 2 O 3 or their hydrated derivatives or alkali silicates and aluminates as well as crystallization accelerators and optionally quaternary ammonium compounds in aqueous alkaline medium; the process is characterized in that an aged but still X-ray amorphous aluminosilicate nucleation gel with an Si / Al atomic ratio of ⁇ 10 is added to the reaction batch as a crystallization accelerator.
  • the Si / A1 atomic ratio in the nucleation gel need not necessarily match that in the crystalline end product. Furthermore, the Al content in the nucleation gel can go towards 0, as in the crystalline end product.
  • the rate of crystallization can be increased considerably by adding the nucleation gel; At the same time, the amount of the nucleation gel added can influence the crystal size of the crystalline end product.
  • the increase in the rate of crystallization also allows the synthesis to be carried out at low temperatures and, instead of the relatively expensive tetrapropylammonium salt, to use cheaper and more easily accessible organic nitrogen compounds or to dispense with the organic substances entirely.
  • An increase in the rate of crystallization can generally be achieved by increasing the rate of nucleation and / or the rate of growth of the crystals.
  • the addition of crystalline nuclei for the synthesis of ZSM-5 is known per se (cf. e.g.
  • the present invention is based on the use of an aged, but not yet crystalline, X-ray amorphous nucleation gel with the Si / Al atomic ratio given above.
  • the quaternary ammonium compound is preferably a tetrapropylammonium salt (TPA + ), in particular the bromide, or the tetrahydropropylammonium hydroxide (TPAOH).
  • aluminosilicate crystals of different sizes are obtained.
  • nucleation gel 4 to 20 wt .-%, based on the Si0 2 content of the finished reaction mixture
  • crystals are obtained in the range of 10 to 100 microns; with larger amounts of nucleation gel (20 to 40% by weight), smaller crystals in the range from 0.5 to 10 ⁇ m are obtained.
  • the crystallite sizes obtained are between about 0.1 and 100 ⁇ m
  • the aged nucleation gel usually in amounts of 4 to 40% by weight, preferably in amounts of 15 to 25% by weight, based on the SiO 2 content of the finished reaction mixture is added.
  • the addition of an old nucleation gel has a decisive advantage over vaccination by crystalline germs, which results from kinetic studies and
  • the aged nucleation gel used according to the invention increases the rate of crystallization and shortens the induction period depending on the aging time.
  • the aging of the nucleation gels can be carried out at room temperature or at a slightly elevated temperature at atmospheric pressure and does not require any additional energy expenditure.
  • the nucleation gel is aged at atmospheric pressure at 15 to 100 ° C, preferably at 20 to 60 ° C, for 2 hours to 100 days, preferably for 10 to 50 days.
  • the crystallization times are reduced by 40 to 90%.
  • the greatly shortened crystallization times have the advantage that larger throughputs can be achieved in a given system and thus economical production is possible.
  • the content of the tetrapropylammonium salts usually used in the reaction mixture can be reduced if nucleating gels aged according to the invention are added.
  • the use of the aged nucleation gels also has the advantage that the sharp shortening of the crystallization times means that the kri can be produced continuously and thus also more economically stallinen alumosilicate is reached.
  • the crystallization time at a reaction temperature of 150 ° C is only 6 hours. In general, temperatures between 40 and 200 ° C can be used.
  • an alkali metal fluoride preferably sodium fluoride or ammonium fluoride, can also be added to the reaction batch, the molar ratio F - / SiO 2 being 0.4 to 1.5.
  • silicalite with a relative degree of crystallization of 100% was obtained after 140 hours.
  • this nucleation gel with a solids content of 32% by weight are added, its amount, based on the total solids in the batch, is 5.7% by weight. Based on SiO 2 in the batch, the proportion of the nucleation gel is 24% by weight.
  • amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.7 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 0.83 g of NaOH, 3.4 g of TPA-Br, 42.2 g of water and 3.6 g of the nucleation gel according to Example 1 were mixed.
  • the nucleation gel had aged for 77 hours at room temperature.
  • an aluminosilicate of the ZSM-5 type with the same degree of crystallization as the sample according to comparative example B was obtained after a crystallization time of 70 hours. This means a time saving of around 41%.
  • amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.7 g of aluminate solution (1000 g of the solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 0.83 g of NaOH, 3.4 g of TPA-Br, 42.2 g of water and 3.6 g of nucleation gel according to Example 1 were mixed.
  • the nucleation gel had been aged for 1200 hours at room temperature.
  • amorphous silica of composition 1 SiO 2 0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of the solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 2.6 g of NaOH, 15 , 0 g of ethylenediamine, 206.5 g of water and 5.0 g of the nucleation gel according to Example 1 were mixed.
  • the nucleation gel had been aged for 54 days at room temperature.
  • the entire reaction mixture thus had the composition: 1 SiO 2 .0.01 AlO - 2. 0.3 NaOH. 1 Eda. 47 H 2 O
  • amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 2.1 g of NaOH, 11.5 g n-butanol, 2.9 g ammonia solution (min. 25%), 90.5 g of water and 5.0 g of the nucleation gel from Example 1 were mixed. The nucleation gel had been aged at room temperature for 60 days.
  • amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 1.2 g of NaOH, 166.8 g of water and 5.0 g of the nucleation gel of Example 1 were mixed.
  • the nucleation gel had aged at room temperature for 67 days.
  • amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 0.8 g of NaOH, 4.6 g of TBA-J, 43.4 g of water and 5.0 g of the nucleation gel from Example.
  • the nucleation gel had aged at room temperature for 14 days.
  • the entire reaction mixture thus had the composition: 1 SiO 2 .0.11 NaOH. 0.05 TBA-J. 10.5 H 2 0 (.0.0009 TPA-Br) (Note: the TPA-Br came from the Nucleation gel)
  • amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.9 g of NaOH, 3.2 g of TPA-Br, 4.6 g of ammonium fluoride (NH 4 F), 42.7 g of water and 3.6 g of the nucleation gel according to Example 1 were mixed.
  • the nucleation gel had been aged for 4 days at room temperature.
  • the entire reaction mixture thus had the composition: 1 SiO 2 .0.11 NaOH. 0.05 TPA-Br. 0.5 NH 4 F.10.5 H 2 O
  • the relative crystallinity was determined by comparison with a reference substance which had been prepared according to US Pat. No. 3,702,886 and was characterized by X-ray analysis.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

Verfahren zur Herstellung von kristallinen zeolithischen Alumosilicaten mit einem Si/Al-Atomverhältnis von >= 10 durch hydrothermale Kristallisation aus einem Reaktionsansatz, der in wäßrig-alkalischem Medium SiO2 und Al2O3 bzw. Derivate dieser Verbindungen, Kristallisationsbeschleuniger und gegebenenfalls quaternäre Ammoniumverbindungen enthält. Dem Reaktionsgemisch wird als Kristallisationsbeschleuniger ein gealtertes, aber noch nicht kristallines, röntgenamorphes Alumosilicat-Keimbildungsgel zugesetzt.Process for the preparation of crystalline zeolitic aluminosilicates with an Si / Al atomic ratio of> = 10 by hydrothermal crystallization from a reaction mixture which contains SiO2 and Al2O3 or derivatives of these compounds, crystallization accelerators and optionally quaternary ammonium compounds in aqueous alkaline medium. An aged, but not yet crystalline, X-ray amorphous aluminosilicate nucleation gel is added to the reaction mixture as a crystallization accelerator.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von kristallinen zeolithischen Alumosilicaten, insbesondere vom Strukturtyp ZSM-5 oder ZSM-11. Bei diesen Alumosilicaten ist das Si/A1-Atomverhältnis im allgemeinen * 10, wobei im Extremfall der Aluminiumgehalt gegen Null gehen kann. Die "Alumosilicate" ohne Aluminium bzw. mit einem geringen Aluminiumgehalt werden als "Silikalite" bezeichnet.The invention relates to a method for producing crystalline zeolitic aluminosilicates, in particular of the ZSM-5 or ZSM-11 structure type. With these aluminosilicates, the Si / A1 atomic ratio is generally * 10, and in extreme cases the aluminum content can go to zero. The "aluminosilicates" without aluminum or with a low aluminum content are referred to as "silicalites".

Die kristallinen zeolithischen Alumosilicate der Strukturtypen ZSM-5 oder ZSM-11 gewinnen in zunehmendem Maße an Bedeutung als Katalysatoren und Katalysatorträger.The crystalline zeolitic aluminosilicates of the structure types ZSM-5 or ZSM-11 are becoming increasingly important as catalysts and catalyst supports.

Zeolithische Alumosilicate vom Strukturtyp ZSM-5 können beispielsweise nach der US-PS 3 702 866 aus Mischungen von reaktivem Si02 und A1203 durch hydrothermale Kristallisation in Gegenwart von Natriumionen und quaternären Ammoniumverbindungen, wie Tetrapropylammoniumsalzen, hergestellt werden. Ein Nachteil dieses und ähnlicher Verfahren besteht darin, daß die Kristallisationszeiten bei wirtschaftliche interessanten Konzentrationen des Tetrapropylammonium-Ions sehr lang sind. Weiterhin entstehen bei diesen Verfahren ZSM-5-Kristalle mit unterschiedlicher Größe, was für die Anwendung als Katalysatoren nachteilig ist.Zeolithic aluminosilicates of the structure type ZSM-5 can be produced, for example, according to US Pat. No. 3,702,866 from mixtures of reactive Si0 2 and A1 2 0 3 by hydrothermal crystallization in the presence of sodium ions and quaternary ammonium compounds, such as tetrapropylammonium salts. A disadvantage of this and similar processes is that the crystallization times are very long at economically interesting concentrations of the tetrapropylammonium ion. Furthermore, ZSM-5 crystals of different sizes are formed in these processes, which is disadvantageous for use as catalysts.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von kristallinen zeolithischen Alumosilikaten zur Verfügung zu stellen, das frei von den Nachteilen des Standes der Technik ist. Insbesondere soll die Geschwindigkeit der hydrothermalen Kristallisation erheblich gesteigert und gleichzeitig Einfluß auf die Kristallgröße des Endproduktes, die im Bereich von 0,1 bis 100 µm liegt, genommen werden.The object of the invention is to provide a process for the production of crystalline zeolitic aluminosilicates which is free from the disadvantages of the prior art. In particular, the rate of hydrothermal crystallization should be increased considerably and at the same time the crystal size of the end product, which is in the range from 0.1 to 100 μm, should be influenced.

Die Erfindung betrifft somit ein Verfahren zur Herstellung von kristallinen zeolithischen Alumosilicaten mit einem Si/Al-Atomverhältnis von * 10 durch hydrothermale Kristallisation aus einem Reaktionsansatz, der in wäßrig-alkalischem Medium Si02 und Al2O3 bzw. deren hydratisierte Derivate oder Alkalisilicate und -aluminate sowie Kristallisationsbeschleuniger und gegebenenfalls quaternäre Ammoniumverbindungen enthält; das Verfahren ist dadurch gekennzeichnet, daß man dem Reaktionsansatz als Kristallisationsbeschleuniger ein gealtertes, aber noch roentgenamorphes Alumosilicat-Keimbildungsgel mit einem Si/Al-Atomverhältnis von ≥ 10 zusetzt.The invention thus relates to a process for the production of crystalline zeolitic aluminosilicates with a Si / Al atomic ratio of * 10 by hydrothermal crystallization from a reaction mixture which contains Si0 2 and Al 2 O 3 or their hydrated derivatives or alkali silicates and aluminates as well as crystallization accelerators and optionally quaternary ammonium compounds in aqueous alkaline medium; the process is characterized in that an aged but still X-ray amorphous aluminosilicate nucleation gel with an Si / Al atomic ratio of ≥ 10 is added to the reaction batch as a crystallization accelerator.

Hierbei braucht das Si/A1-Atomverhältnis im Keimbildungsgel nicht unbedingt mit dem im kristallinen Endprodukt übereinzustimmen. Ferner kann der Al-Gehalt im Keimbildungsgel wie im kristallinen Endprodukt gegen 0 gehen.Here, the Si / A1 atomic ratio in the nucleation gel need not necessarily match that in the crystalline end product. Furthermore, the Al content in the nucleation gel can go towards 0, as in the crystalline end product.

Durch den Zusatz des Keimbildungsgels kann die Geschwindigkeit der Kristallisation erheblich gesteigert werden; gleichzeitig kann über die Menge des zugesetzten Keimbildungsgels Einfluß auf die Kristallgröße des kristallinen Endproduktes genommen werden. Die Erhöhung der Kristallisationsgeschwindigkeit erlaubt es weiterhin, die Synthese bei niedrigen Temperaturen ablaufen zu lassen und statt des verhältnismäßig kostspieligen Tetrapropylammoniumsalzes billigere und leichter zugängliche organische Stickstoffverbindungen zu verwenden oder auf die organischen Substanzen ganz zu verzichten.The rate of crystallization can be increased considerably by adding the nucleation gel; At the same time, the amount of the nucleation gel added can influence the crystal size of the crystalline end product. The increase in the rate of crystallization also allows the synthesis to be carried out at low temperatures and, instead of the relatively expensive tetrapropylammonium salt, to use cheaper and more easily accessible organic nitrogen compounds or to dispense with the organic substances entirely.

Eine Erhöhung der Kristallisationsgeschwindigkeit ist im allgemeinen durch eine Erhöhung der Keimbildungsgeschwindigkeit und/oder der Wachstumsgeschwindigkeit der Kristalle zu erreichen. Der Zusatz von kristallinen Keimen zur Synthese von ZSM-5 ist an sich bekannt (vgl. z.B.An increase in the rate of crystallization can generally be achieved by increasing the rate of nucleation and / or the rate of growth of the crystals. The addition of crystalline nuclei for the synthesis of ZSM-5 is known per se (cf. e.g.

US-PS 4 175 114, DE-OS 29 35 123). Die vorliegende Erfindung beruht im Gegensatz dazu auf der Anwendung eines gealterten, aber noch nicht kristallinen, roentgenamorphen Keimbildungsgels mit dem vorstehend angegebenen Si/Al-Atomverhältnis.US-PS 4 175 114, DE-OS 29 35 123). In contrast, the present invention is based on the use of an aged, but not yet crystalline, X-ray amorphous nucleation gel with the Si / Al atomic ratio given above.

Vorzugsweise verwendet man ein gealtertes Keimbildungsgel der Zusammensetzung (auf molarer Basis) SiO2/AlO- 2 ≥ 20, HO /Si02 = 0,05 bis 1,0, quaternäre Ammoniumverbindung/ Si02 = 0,0 bis 2,0, vorzugsweise 0,01 bis 2,0, H20/Si02 = 10 bis 1000. Hierbei stellt die quaternäre Ammoniumverbindung vorzugsweise ein Tetrapropylammoniumsalz (TPA+), insbesondere das Bromid, oder das Tetrahydropropylammoniumhydroxid (TPAOH) dar. Nach einer Anwandlung des vorstehend beschriebenen Verfahrens kann man statt der quaternären Ammoniumverbindungen billigere und leichter zugängliche Stickstoffverbindungen, z.B. Amine, vorzugsweise ein Alkylendiamin, oder Gemische aus Alkoholen mit Ammoniak, verwenden. Es können ein- oder mehrwertige Alkohole verwendet werden.It is preferred to use an aged nucleating gel of the composition (on a molar basis) SiO 2 / AlO - 2 20 20, HO / Si0 2 = 0.05 to 1.0, quaternary ammonium compound / Si0 2 = 0.0 to 2.0, preferably 0.01 to 2.0, H 2 0 / Si0 2 = 10 to 1000. Here, the quaternary ammonium compound is preferably a tetrapropylammonium salt (TPA + ), in particular the bromide, or the tetrahydropropylammonium hydroxide (TPAOH). After a modification of the one described above Process can be used instead of the quaternary ammonium compounds cheaper and more accessible nitrogen compounds, such as amines, preferably an alkylenediamine, or mixtures of alcohols with ammonia. Mono- or polyhydric alcohols can be used.

Je nach der dem Reaktionsansatz zugesetzten Menge an Keimbildungsgel werden Alumosilicat-Kristalle unterschiedlicher Größe erhalten. Mit kleinen Mengen an Keimbildungsgel (4 bis 20 Gew.-%, bezogen auf den Si02-Gehalt des fertigen Reaktionsansatzes) erhält man Kristalle im Bereich von 10 bis 100 µm; mit größeren Mengen Keimbildungsgel (20 bis 40 Gew.-%) erhält man kleinere Kristalle im Bereich von 0,5 bis 10 µm. Im allgemeinen liegen die erhaltenen Kristallitgrößen zwischen etwa 0,1 und 100 µm, wobei das gealterte Keimbildungsgel üblicherweise in Mengen von 4 bis 40 Gew.-%, vorzugsweise in Mengen von 15 bis 25 Gew.-%, bezogen auf den Si02-Gehalt des fertigen Reaktionsansatzes zugesetzt wird. Der Zusatz eines alterten Keimbildungsgels hat gegenüber der Impfung durch kristalline Keime einen entscheidenden Vorteil, der sich aus kinetischen Untersuchungen ergibt undDepending on the amount of nucleation gel added to the reaction mixture, aluminosilicate crystals of different sizes are obtained. With small amounts of nucleation gel (4 to 20 wt .-%, based on the Si0 2 content of the finished reaction mixture) crystals are obtained in the range of 10 to 100 microns; with larger amounts of nucleation gel (20 to 40% by weight), smaller crystals in the range from 0.5 to 10 µm are obtained. In general, the crystallite sizes obtained are between about 0.1 and 100 μm, the aged nucleation gel usually in amounts of 4 to 40% by weight, preferably in amounts of 15 to 25% by weight, based on the SiO 2 content of the finished reaction mixture is added. The addition of an old nucleation gel has a decisive advantage over vaccination by crystalline germs, which results from kinetic studies and

in der beigefügten Zeichnung dargestellt ist. Für einen Ansatz ohne Keime beobachtet man eine Induktionsperiode, die ie nach den Bedingungen 10 bis 60 Stunden betragen kann. Nach dieser Induktionsperiode erfolgt ein relativ schnelles Kristallwachstum. Bei Zusatz von kristallinen Keimen beginnt das Kristallwachstum sofort, setzt sich dann aber mit einer geringeren Wachstumsgeschwindigkeit fort. Zur Erzielung einer möglichst großen Wachstumsgeschwindigkeit sind sehr kleine Keime erforderlich. Das erfindungsgemäß verwendete, gealterte Keimbildungsgel erhöht die Kristallisationsgeschwindigkeit und verkürzt die Induktionsperiode je nach Alterungszeit. Das Altern der Keimbildungsgele kann bei Raumtemperatur oder bei leicht erhöhter Temperatur bei atmosphärischem Druck durchgeführt werden und erfordert keinen zusätzlichen Energieaufwand. Üblicherweise wird das Keimbildungsgel bei atmosphärischem Druck bei 15 bis 100°C vorzugsweise bei 20 bis 60°C, über 2 Stunden bis 100 Tage, vorzugsweise über 10 bis 50 Tage, gealtert.is shown in the accompanying drawing. For an approach without germs, an induction period is observed, which can be 10 to 60 hours under the conditions. After this induction period, crystal growth is relatively rapid. When crystalline seeds are added, crystal growth begins immediately, but then continues at a slower growth rate. Very small germs are required to achieve the highest possible growth rate. The aged nucleation gel used according to the invention increases the rate of crystallization and shortens the induction period depending on the aging time. The aging of the nucleation gels can be carried out at room temperature or at a slightly elevated temperature at atmospheric pressure and does not require any additional energy expenditure. Usually the nucleation gel is aged at atmospheric pressure at 15 to 100 ° C, preferably at 20 to 60 ° C, for 2 hours to 100 days, preferably for 10 to 50 days.

Bei der Anwendung der erfindungsgemäßen Keimbildungsgele verkürzen sich die Kristallisationszeiten um 40 bis 90 %. Die stark verkürzten Kristallisationszeiten haben den Vorteil, daß bei einer gegebenen Anlage größere Durchsätze erzielt werden können und somit eine wirtschaftliche Herstellung möglich ist.When using the nucleation gels according to the invention, the crystallization times are reduced by 40 to 90%. The greatly shortened crystallization times have the advantage that larger throughputs can be achieved in a given system and thus economical production is possible.

Weiterhin läßt sich der Gehalt an den üblicherweise verwendeten Tetrapropylammoniumsalzen im Reaktionsansatz senken, wenn erfindungsgemäß gealterte Keimbildungsgele zugesetzt werden. Die Anwendung der gealterten Keimbildungsgele bringt außerdem den Vorteil, daß durch die starke Verkürzung der Kristallisationszeiten eine kontinuierliche und damit auch eine wesentlich wirtschaftlichere Herstellung der kristallinen Alumosilicate erreicht wird. So beträgt z.B. die Kristallisationszeit bei einer Reaktionstemperatur von 150°C nur noch 6 Stunden. Im allgemeinen kann bei Temperaturen zwischen 40 und 200°C gearbeitet werden.Furthermore, the content of the tetrapropylammonium salts usually used in the reaction mixture can be reduced if nucleating gels aged according to the invention are added. The use of the aged nucleation gels also has the advantage that the sharp shortening of the crystallization times means that the kri can be produced continuously and thus also more economically stallinen alumosilicate is reached. For example, the crystallization time at a reaction temperature of 150 ° C is only 6 hours. In general, temperatures between 40 and 200 ° C can be used.

Ein bevorzugt verwendetes gealtertes Keimbildungsgel hat folgende Zusammensetzung (auf molarer Basis) : SiO2/Al2O3 ≥ 5, HO-/SiO2 = 10-10 bis 1,0, quaternäre Ammoniumverbindung/ SiO2 = 0,01 bis 2,0, H2O/SiO2 = 0,7 bis 3000, Me/SiO2 = 0,3 bis 3,0, wobei Me ein Alkali- oder Erdalkalimetall-Kation darstellt. Ferner kann man dem Reaktionsansatz zusätzlich zu dem gealterten Keimbildungsgel ein Alkalifluorid, vorzugsweise Natriumfluorid oder Ammoniumfluorid, zusetzen, wobei das Molverhältnis F-/SiO2 0,4 bis 1,5 betragen kann.A preferred used nucleation gel has the following composition (on a molar basis): SiO 2 / Al 2 O 3 ≥ 5, HO - / SiO 2 = 10 -10 to 1.0, quaternary ammonium compound / SiO 2 = 0.01 to 2, 0, H 2 O / SiO 2 = 0.7 to 3000, Me / SiO 2 = 0.3 to 3.0, where Me is an alkali or alkaline earth metal cation. In addition to the aged nucleation gel, an alkali metal fluoride, preferably sodium fluoride or ammonium fluoride, can also be added to the reaction batch, the molar ratio F - / SiO 2 being 0.4 to 1.5.

Die Erfindung ist durch die nachstehenden Beispiele in nicht einschränkender Weise erläutert.The invention is illustrated in a non-limiting manner by the examples below.

Vergleichsbeispiel AComparative Example A Herstellung eines SilikalitsManufacture of a silicalite

17,2 g amorphe Kieselsäure der Zusammensetzung 1 Si02. 0,5 H20 wurden mit 1,1 g NaOH, 3,36 g TPA-Br und 45 g Wasser vermengt. Der Reaktionsansatz hatte die molare Zusammensetzung:

  • 1 SiO2. 0,11 NaOH. 0,05 TPA-Br. 10,5 H20
17.2 g of amorphous silica of the composition 1 Si0 2 . 0.5 H 2 0 was mixed with 1.1 g NaOH, 3.36 g TPA-Br and 45 g water. The reaction mixture had the molar composition:
  • 1 SiO 2 . 0.11 NaOH. 0.05 TPA Br. 10.5 H 2 0

Bei einer Kristallisationstemperatur von 85°C wurde nach 140 Std. Silikalit mit einem relativen Kristallisationsgrad von 100 % (ermittelt aus dem Röntgendiagramm) erhalten.At a crystallization temperature of 85 ° C., silicalite with a relative degree of crystallization of 100% (determined from the X-ray diagram) was obtained after 140 hours.

Beispiel 1example 1 Herstellung eines kristallinen Alumosilicats vom SilikalittypProduction of a crystalline silicate type aluminosilicate

16,3 g amorphe Kieselsäure der Zusammensetzung 1 SiO2. 0,5 H2O wurden mit 0,9 g NaOH, 3,2 g TPA-Br, 42,7 g Wasser und 3,6 g Keimbildungsgel vermengt. Zur Herstellung des Keimbildungsgels wurden 6,9 g amorphe Kieselsäure der Zusammensetzung 1 SiO2· 0,5 H20 mit 1,6 g NaCH, 1,3 g TPA-Br und 18 g H20 unter Rühren bei Raumtemperatur vereinigt und 46 Std. gealtert. Das Keimbildungsgel hat die nachstehende molare Zusammensetzung:

  • 1 SiO2· 0,39 NaOH· 0,05 TPA-Br 10,5 H20
16.3 g of amorphous silica with the composition 1 SiO 2 . 0.5 H 2 O was mixed with 0.9 g NaOH, 3.2 g TPA-Br, 42.7 g water and 3.6 g nucleation gel. To produce the nucleation gel, 6.9 g of amorphous silica of the composition 1 SiO 2 .0.5 H 2 0 were combined with 1.6 g NaCH, 1.3 g TPA-Br and 18 g H 2 0 with stirring at room temperature and 46 Hours aged. The nucleation gel has the following molar composition:
  • 1 SiO 2 · 0.39 NaOH · 0.05 TPA-Br 10.5 H 2 0

Der gesamte Reaktionsansatz hatte somit die Zusammensetzung:

  • 1 SiO2 · 0,11 NaOH· 0,05 TPA-Br · 10,5 H20.
The entire reaction batch thus had the following composition:
  • 1 SiO 2 · 0.11 NaOH · 0.05 TPA-Br · 10.5 H 2 0.

Bei einem Zusatz von 3,6 g dieses Keimbildungsgels mit einem Feststoffgehalt von 32 Gew.% beträgt seine Menge, bezogen auf den gesamten Feststoff im Ansatz, 5,7 Gew.%. Bezogen auf SiO2 im Ansatz, liegt der Anteil des Keimbildungsgels bei 24 Gew.%.If 3.6 g of this nucleation gel with a solids content of 32% by weight are added, its amount, based on the total solids in the batch, is 5.7% by weight. Based on SiO 2 in the batch, the proportion of the nucleation gel is 24% by weight.

Bei einer Kristallisationstemperatur von 85°C wurde nach 70 Std. ein kristallines Alumosilicat vom Silikalittyp mit dem gleiche Kristallisationsgrad wie im Vergleichsbeispiel A erhalten. Dies bedeutet eine Zeitersparnis von 50 %.At a crystallization temperature of 85 ° C., a crystalline aluminosilicate of the silicalite type with the same degree of crystallization as in Comparative Example A was obtained after 70 hours. This means a time saving of 50%.

Beispiel 2Example 2 Herstellung eines kristallinen Alumosilicats vom SilikalittypProduction of a crystalline silicate type aluminosilicate

16,3 g amorphe Kieselsäure der Zusammensetzung 1 SiO2· 0,5 H20 wurden mit 0,9 g NaOH, 3,2 g TPA-Br, 42,7 g Wasser und 3,6 g des in Beispiel 1 beschriebenen Keimbildungsgels vermengt. Das Keimbildungsgel war 1200 Std. bei Raumtemperatur gealtert worden.16.3 g of amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.9 g of NaOH, 3.2 g of TPA-Br, 42.7 g of water and 3.6 g of the nucleation gel described in Example 1 blended. The nucleation gel had been aged for 1200 hours at room temperature.

Der gesamte Reaktionsansatz besaß somit die Zusammensetzung: 1 SiO2 · 0,11 NaOH · 0,05 TPA-Br. 10,5 H20The entire reaction mixture thus had the composition: 1 SiO 2 .0.11 NaOH. 0.05 TPA-Br. 10.5 H 2 0

Bei einer Kirstallisationstemperatur von 85°C wurde nach einer Kristallisationszeit von 25 Std. ein Silicat des ZSM-5-Typs (Silikalit) mit dem gleichen Kristallisationsgrad wie im Vergleichsbeispiel A erhalten. Dies bedeutet eine Zeitersparnis von etwa 82 %.At a crystallization temperature of 85 ° C., a silicate of the ZSM-5 type (silicalite) with the same degree of crystallization as in Comparative Example A was obtained after a crystallization time of 25 hours. This means a time saving of around 82%.

Vergleichsbeispiel BComparative Example B Herstellung eines Zeolithen vom ZSM-5-TypProduction of a ZSM-5 type zeolite

17,2 amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,5 H2O wurden mit 0,71 g Aluminatlösung (1000 g Lösung enthalten 100 g NaOH, 205 g NaAlO2 und 695 g Wasser), 1,03 g NaOH, 3,4 g TPA-Br und 44,5 g Wasser vermengt. Der Reaktionsansatz hatte die Zusammensetzung:

  • 1 SiO2 0,007 AlO- 2· 0,11 NaOH · 0,05 TPA-Br . 10,5 H2O
17.2 amorphous silica of the composition 1 SiO 2 .0.5 H 2 O was mixed with 0.71 g of aluminate solution (1000 g of solution contain 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 1.03 g of NaOH, 3 , 4 g TPA-Br and 44.5 g water mixed. The reaction mixture had the following composition:
  • 1 SiO 2 0.007 AlO - 2 · 0.11 NaOH · 0.05 TPA-Br. 10.5 H 2 O

Bei einer Kristallisationstemperatur von 90°C wurde nach 130 Std. ZSM-5 mit einem relativen Kristallisationsgrad von 100 % (ermittelt ausRöntgenbeugungsdiagrammen) erhalten.At a crystallization temperature of 90 ° C ZSM-5 with a relative degree of crystallization of 100% (determined from X-ray diffraction patterns) was obtained after 130 hours.

Beispiel 3Example 3 Herstellung von kristallinem Alumosilicat des ZSM-5-Typs mit Hilfe von aluminiumfreiem KeimbildungsgelProduction of crystalline aluminosilicate of the ZSM-5 type with the aid of aluminum-free nucleation gel

16,3 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,5 H20 wurden mit 0,7 g Aluminatlösung (1000 g Lösung enthielten 100 g NaOH, 205 g NaAlO2 und 695 g Wasser), 0,83 g NaOH, 3,4 g TPA-Br, 42,2 g Wasser und 3,6 g des Keimbildungsgels nach Beispiel 1 vermengt. Das Keimbildungsgel war 77 Std. bei Raumtemperatur gealtert worden.16.3 g of amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.7 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 0.83 g of NaOH, 3.4 g of TPA-Br, 42.2 g of water and 3.6 g of the nucleation gel according to Example 1 were mixed. The nucleation gel had aged for 77 hours at room temperature.

Der gesamte Reaktionsansatz hatte somit die Zusammensetzung; 1 SiO2 0,007 AlO- 2 · 0,11 NaOH · 0,05 TPA-Br . 10,5 H2OThe entire reaction batch thus had the composition; 1 SiO2 0.007 AlO - 2 · 0.11 NaOH · 0.05 TPA-Br. 10.5 H 2 O

Bei einer Kristallisationstemperatur von 90°C wurde nach einer Kristallisationszeit von 70 Std. ein Alumosilicat des ZSM-5-Typs mit dem gleichen Kristallisationsgrad wie die Probe nach dem Vergleichsbeispiel B erhalten. Dies bedeutet eine Zeitersparnis von etwa 41 %.At a crystallization temperature of 90 ° C., an aluminosilicate of the ZSM-5 type with the same degree of crystallization as the sample according to comparative example B was obtained after a crystallization time of 70 hours. This means a time saving of around 41%.

Beispiel 4Example 4 Herstellung von kristallinen Alumosilicaten des ZSM-5-Typs mit Hilfe von aluminiumfreiem KeimbildungsgelProduction of crystalline aluminosilicates of the ZSM-5 type with the aid of aluminum-free nucleation gel

16,3 amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,5 H20 wurden mit 0,7 g Aluminatlösung (1000 g der Lösung enthielten 100 g NaOH, 205 g NaAlO2 und 695 g Wasser), 0,83 g NaOH, 3,4 g TPA-Br, 42,2 g Wasser und 3,6 g Keimbildungsgel nach Beispiel 1 vermengt. Das Keimbildungsgel war 1200 Std. bei Raumtemperatur gealtert worden.16.3 amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.7 g of aluminate solution (1000 g of the solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 0.83 g of NaOH, 3.4 g of TPA-Br, 42.2 g of water and 3.6 g of nucleation gel according to Example 1 were mixed. The nucleation gel had been aged for 1200 hours at room temperature.

Bei einer Kristallisationstemperatur von 90°C wurde nach einer Kristallisationszeit von 20 Std. ein Alumosilicat des ZSM-5-Typs mit dem gleichen Kristallisationsgrad das Produkt nach Vergleichsbeispiel B erhalten. Dies bedeutet eine Zeitersparnis von etwa 85 %.At a crystallization temperature of 90 ° C., after a crystallization time of 20 hours, an aluminosilicate of the ZSM-5 type with the same degree of crystallization was obtained the product according to comparative example B. This means a time saving of around 85%.

Vergleichsbeispiel CComparative Example C Herstellung von kristallinem Alumosilicat des ZSM-5-Typs unter Verwendung von EthylendiaminPreparation of ZSM-5 type crystalline aluminosilicate using ethylenediamine

15,5 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,1 H20 wurden mit 1,0 g Aluminatlösung (1000 g Lösung enthielten 100 g NaOH, 205 g NaAl02 ind 695 g Wasser), 2,9 g NaOn, 15,0 g Ethylendiamin und 210 g Wasser vermengt. Der Reaktionsansatz hatte die Zusammensetzung: 1 SiO2 · 0,01 AlO- 2 · 0,3 NaOH · 1 Eda · 47 H2O15.5 g of amorphous silica of the composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAl0 2 and 695 g of water), 2.9 g of NaOn, 15.0 g of ethylenediamine and 210 g of water were mixed. The reaction mixture had the composition: 1 SiO 2 .01 AlO - 2. 0.3 NaOH. 1 Eda. 47 H 2 O

Nach 140 Std. bei einer Kristallisationstemperatur von 150°C wurde ein Alumosilicat des ZSM-5-Typs mit einem relativen Kristallisationsgrad von 60 % erhalten.After 140 hours at a crystallization temperature of 150 ° C., an aluminosilicate of the ZSM-5 type was obtained with a relative degree of crystallization of 60%.

Beispiel 5Example 5 Herstellung von kristallinem Alumosilicat des ZSM-5-Typs unter Verwendung von Ethylendiamin und KeimbildungsgelPreparation of ZSM-5 type crystalline aluminosilicate using ethylenediamine and nucleation gel

14,4 g amorphe Kieselsäure der Zusammensetzung 1 Si02 0,1 H20 wurden mit 1,0 g Aluminatlösung (1000 g der Lösung enthielten 100 g NaOH, 205 g NaAl02 und 695 g Wasser), 2,6 g NaOH, 15,0 g Ethylendiamin, 206,5 g Wasser und 5,0 g des Keimbildungsgels nach Beispiel 1 vermengt. Das Keimbildungsgel war 54 Tage bei Raumtemperatur gealtert worden. Der gesamte Reaktionsansatz hatte somit die Zusammensetzung: 1 SiO2 · 0,01 AlO- 2 · 0,3 NaOH · 1 Eda · 47 H2O14.4 g of amorphous silica of composition 1 SiO 2 0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of the solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 2.6 g of NaOH, 15 , 0 g of ethylenediamine, 206.5 g of water and 5.0 g of the nucleation gel according to Example 1 were mixed. The nucleation gel had been aged for 54 days at room temperature. The entire reaction mixture thus had the composition: 1 SiO 2 .0.01 AlO - 2. 0.3 NaOH. 1 Eda. 47 H 2 O

Nach 140 Std. bei einer Kristallisationstemperatur von 150°C wurde ein Alumosilicat des ZSM-5-Typs mit einem relativen Kristallisationsgrad von 80 % erhalten.After 140 hours at a crystallization temperature of 150 ° C., an aluminosilicate of the ZSM-5 type with a relative degree of crystallization of 80% was obtained.

Vergleichsbeispiel DComparative Example D Herstellung von kristallinem Alumosilicat des ZSM-5-Typs unter Verwendung von n-Butanol und AmmoniakPreparation of ZSM-5 type crystalline aluminosilicate using n-butanol and ammonia

15,5 g amorphe Kieselsäure der Zusammensetzung 1 Si02 0,1 H20 wurden mit 1,0 g Aluminatlösung (1000 g Lösung enthielten 100 g NaOH, 205 g NaAlO2 und 695 g Wasser), 2,4 g NaOH, 11,5 g n-Butanol, 2,9 g Ammoniak-Lösung (min. 25%ig) und 94 g Wasser vermengt. Der Reaktionsansatz hatte die Zusammensetzung:

  • 1 SiO · 0,01 AlO- 2 · 0,25 NaOH · 0,62 C4H9OH · 0,17 NH3 · 21 H2O
15.5 g of amorphous silica of composition 1 SiO 2 0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 2.4 g of NaOH, 11 5 g of n-butanol, 2.9 g of ammonia solution (min. 25%) and 94 g of water are mixed. The reaction mixture had the following composition:
  • 1 SiO. 0.01 AlO - 2. 0.25 NaOH. 0.62 C 4 H 9 OH. 0.17 NH 3. 21 H 2 O

Nach 72 Std. bei einer Kristallisationstemperatur von 150°C wurde ein Alumosilicat des ZSM-5-Typs mit einem relativen Kristallisationsgrad von 60 % erhalten.After 72 hours at a crystallization temperature of 150 ° C., an aluminosilicate of the ZSM-5 type with a relative degree of crystallization of 60% was obtained.

Beispiel 6Example 6 Herstellung von kristallinem Alumosilicat des ZSM-5-Typs unter Verwendung von n-Butanol, Ammoniak und KeimbildungsgelProduction of ZSM-5 type crystalline aluminosilicate using n-butanol, ammonia and nucleation gel

14,4 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,1 H20 wurden mit 1,0 g Aluminatlösung (1000 g Lösung enthielten 100 g NaOH, 205 g NaAlO2 und 695 g Wasser), 2,1 g NaOH, 11,5 g n-Butanol, 2,9 g Ammoniak-Lösung (min. 25%ig), 90,5 g Wasser und 5,0 g des Keimbildungsgels vom Beispiel 1 vermengt. Das Keimbildungsgel war 60 Tage bei Raumtemperatur gealtert worden.14.4 g of amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 2.1 g of NaOH, 11.5 g n-butanol, 2.9 g ammonia solution (min. 25%), 90.5 g of water and 5.0 g of the nucleation gel from Example 1 were mixed. The nucleation gel had been aged at room temperature for 60 days.

Der gesamte Raktionsansatz hatte somit die Zusammensetzung:

  • 1 SiO2 · 0,01 AlO- 2 · 0,25 NaOH ' 0,62 C4H9OH · 0,17 NH3 · 21 H2O
The entire ratchet approach thus had the following composition:
  • 1 SiO 2 .01 AlO - 2 .0.25 NaOH ' 0.62 C 4 H 9 OH. 0.17 NH 3 .21 H 2 O

Nach 20 Std. bei einer Kristallisationstemperatur von 150°C wurde ein Alumosilicat vom ZSM-5-Typ mit dem relativen Kristallisationsgrad des Produkts nach dem Vergleichsbeispiel B erhalten. Dies bedeutet eine Erhöhung der Kristallinität und zusätzlich eine Verkürzung der Kristallisationszeit.After 20 hours at a crystallization temperature of 150 ° C., a ZSM-5 type aluminosilicate with the relative degree of crystallization of the product according to Comparative Example B was obtained. This means an increase in the crystallinity and additionally a shortening of the crystallization time.

Vergleichsbeispiel EComparative Example E Herstellung von kristallinem Alumosilicat des ZSM-5-Typs in Abwesenheit von organischen SubstanzenProduction of ZSM-5 type crystalline aluminosilicate in the absence of organic substances

15,5 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,1 H20 wurden mit 1,0 g Aluminatlösung (1000 g Lösung enthielten 100 g NaOH, 205 g NaAl02 und 695 g Wasser), 1,5 g NaOH und 170,3 g Wasser vermengt. Der Reaktionsansatz hatte die Zusammensetzung:

  • 1 SiO2 · 0,01 AlO- 2 · 0,16 NaOH · 40 H2O
15.5 g of amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAl0 2 and 695 g of water), 1.5 g of NaOH and 170.3 g of water mixed. The reaction mixture had the following composition:
  • 1 SiO 2 .01 AlO - 2. 0.16 NaOH. 40 H 2 O

Nach 72 Std. bei einer Kristallisationstemperatur von 200°C wurde ein Alumosilicat des ZSM-5-Typs mit einem relativen Kristallisationsgrad von 5 - 10 % erhalten.After 72 hours at a crystallization temperature of 200 ° C., an aluminosilicate of the ZSM-5 type with a relative degree of crystallization of 5-10% was obtained.

Beispiel 7Example 7 Herstellung von kristallinem Alumosilicat des ZSM-5-Typs in Abwesenheit von organischen Substanzen und unter Verwendung des KeimbildungsgelsPreparation of ZSM-5 type crystalline aluminosilicate in the absence of organic substances and using the nucleation gel

14,4 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,1 H20 wurden mit 1,0 g Aluminatlösung (1000 g Lösung enthielten 100 g NaOH, 205 g NaAlO2 und 695 g Wasser), 1,2 g NaOH, 166,8 g Wasser und 5,0 g des Keimbildungsgels von Beispiel 1 vermengt. Das Keimbildungsgel war 67 Tage bei Raumtemperatur gealtert worden.14.4 g of amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.0 g of aluminate solution (1000 g of solution contained 100 g of NaOH, 205 g of NaAlO 2 and 695 g of water), 1.2 g of NaOH, 166.8 g of water and 5.0 g of the nucleation gel of Example 1 were mixed. The nucleation gel had aged at room temperature for 67 days.

Der gesamte Reaktionsansatz hatte somit die Zusammensetzung: 1 SiO2 · 0,01 AlO- 2 · 0,16 NaOH · 40 H20 (· 0,0009 TPA-Br) (Anm.: Das TPA-Br stammt aus dem Keimbildungsgel nach Beispiel 1).The entire reaction mixture thus the composition: - 2 · 0, 1 × 40 6 NaOH H20 (0.0009 · TPA - B r) 1 SiO 2 · 0.01 AlO (note .: The TPA-Br comes after out of the nucleating gel Example 1).

Nach 72 Std. bei einer Kristallisationstemperatur von 200°C wurde ein Alumosilicat des ZSM-5-Typs mit einem relativen Kristallisationsgrad von 15 - 20 % erhalten.After 72 hours at a crystallization temperature of 200 ° C., an aluminosilicate of the ZSM-5 type with a relative degree of crystallization of 15-20% was obtained.

Vergleichsbeispiel FComparative Example F ZSM-11-HerstellungZSM-11 manufacture

15,5 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,1 H20 wurden mit 1,1 g NaOH, 4,6 g Tetrabutylammoniumjodid (TBA-J) und 46,9 g Wasser vermengt. Der Reaktionsansatz hatte die Zusammensetzung:

  • 1 SiO2 · 0,11 NaOH · 0,05 TBA-J . 10,5 H20
15.5 g of amorphous silica of the composition 1 SiO 2 .0.1 H 2 0 were mixed with 1.1 g of NaOH, 4.6 g of tetrabutylammonium iodide (TBA-J) and 46.9 g of water. The reaction mixture had the following composition:
  • 1 SiO 2 · 0.11 NaOH · 0.05 TBA-J. 10.5 H 2 0

Nach 240 Std. bei einer Kristallisationstemperatur von 90°C wurde ein ZSM-11 mit einem relativen Kristallisationsgrad von 100 % (ermittelt aus Röntgenbeugungsdiagrammen) erhalten.After 240 hours at a crystallization temperature of 90 ° C., a ZSM-11 with a relative degree of crystallization of 100% (determined from X-ray diffraction diagrams) was obtained.

Beispiel 8Example 8 Herstellung von kristallinem Alumosilicat des ZSM-11-Typs unter Verwendung von KeimbildungsgelPreparation of ZSM-11 type crystalline aluminosilicate using nucleation gel

14,4 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,1 H20 wurden mit 0,8 g NaOH, 4,6 g TBA-J, 43,4 g Wasser und 5,0 g des Keimbildungsgels von Beispiel vermengt. Das Keimbildungsgel war 14 Tage bei Raumtemperatur gealtert worden.14.4 g of amorphous silica of composition 1 SiO 2 .0.1 H 2 0 were mixed with 0.8 g of NaOH, 4.6 g of TBA-J, 43.4 g of water and 5.0 g of the nucleation gel from Example. The nucleation gel had aged at room temperature for 14 days.

Der gesamte Reaktionsansatz hatte somit die Zusammensetzung: 1 SiO2 · 0,11 NaOH · 0,05 TBA-J · 10,5 H20 (· 0,0009 TPA-Br) (Anm.: das TPA-Br stammte aus dem Keimbildungsgel)The entire reaction mixture thus had the composition: 1 SiO 2 .0.11 NaOH. 0.05 TBA-J. 10.5 H 2 0 (.0.0009 TPA-Br) (Note: the TPA-Br came from the Nucleation gel)

Nach 115 Std. bei einer Kristallisationstemperatur von 90°C wurde ein Alumosilicat des ZSM-11-Typs mit dem gleichen Kristallisationsgrad wie das Produkt nach Vergleichsbeispiel F erhalten. Dies bedeutet eine Zeitersparnis von etwa 52 %.After 115 hours at a crystallization temperature of 90 ° C., an aluminosilicate of the ZSM-11 type was obtained with the same degree of crystallization as the product according to Comparative Example F. This means a time saving of around 52%.

Beispiel 9Example 9 Herstellung von aluminiumfreiem kristallinem Silicat des ZSM-5-Typs (Silikalit) unter Verwendung von Keimbildungsgel und in Anwesenheit von NH4FPreparation of ZSM-5 type (silicalite) aluminum-free crystalline silicate using nucleation gel and in the presence of NH 4 F

16,3 g amorphe Kieselsäure der Zusammensetzung 1 SiO2 · 0,5 H20 wurden mit 0,9 g NaOH, 3,2 g TPA-Br, 4,6 g Ammoniumfluorid (NH4F), 42, 7 g Wasser und 3,6 g des Keimbildungsgels nach Beispiel 1 vermengt. Das Keimbildungsgel war 4 Tage bei Raumtemperatur gealtert worden.16.3 g of amorphous silica of composition 1 SiO 2 .0.5 H 2 0 were mixed with 0.9 g of NaOH, 3.2 g of TPA-Br, 4.6 g of ammonium fluoride (NH 4 F), 42.7 g of water and 3.6 g of the nucleation gel according to Example 1 were mixed. The nucleation gel had been aged for 4 days at room temperature.

Der gesamte Reaktionsansatz hatte somit die Zusammensetzung: 1 SiO2 · 0,11 NaOH · 0,05 TPA-Br . 0,5 NH4F · 10,5 H2OThe entire reaction mixture thus had the composition: 1 SiO 2 .0.11 NaOH. 0.05 TPA-Br. 0.5 NH 4 F.10.5 H 2 O

Nach 50 Std. bei einer Kristallisationstemperatur von 90°C wurde ein grobkristallines Alumosilicat des Silikalittyps (Teilchengröße etwa 40 bis 60 µm) mit einem relativen Kristallisationsgrad von 100 % erhalten.After 50 hours at a crystallization temperature of 90 ° C., a coarsely crystalline aluminosilicate of the silicalite type (particle size about 40 to 60 μm) with a relative degree of crystallization of 100% was obtained.

Erläuterungen zur ZeichnungExplanations of the drawing

Figure imgb0001
Figure imgb0001

Die relative Kristallinität wurde durch Vergleich mit einer Referenzsubstanz, die nach der US-PS 3 702 886 hergestellt und röntgenographisch charakterisiert worden war, bestimmt.The relative crystallinity was determined by comparison with a reference substance which had been prepared according to US Pat. No. 3,702,886 and was characterized by X-ray analysis.

Claims (9)

1. Verfahren zur Herstellung von kristallinen zeolithischen Alumosilicaten mit einem Si/A1-Atomverhältnis von ≥ 10 durch hydrothermale Kristallisation aus einem Reaktionsansatz, der in wäßrig-alkalischem Medium Si02 und A1203 bzw. deren hydratisierte Derivate oder Alkali-Silicate und -Aluminate, Kristallisationsbeschleuniger und gegebenenfalls quaternäre Ammoniumverbindungen enthält, dadurch gekennzeichnet, daß man dem Reaktionsansatz als Kristallisationsbeschleuniger ein gealtertes, aber noch roentgenamorphes Alumosilicat-Keimbildungsgel mit einem Si/A1-Atomverhältnis von ≥ 10 zusetzt.1. Process for the preparation of crystalline zeolitic aluminosilicates with an Si / A1 atomic ratio of ≥ 10 by hydrothermal crystallization from a reaction mixture which in aqueous alkaline medium Si0 2 and A1 2 0 3 or their hydrated derivatives or alkali silicates and - Contains aluminates, crystallization accelerators and optionally quaternary ammonium compounds, characterized in that an aged, but still X-ray amorphous, alumosilicate nucleation gel with an Si / A1 atomic ratio of ≥ 10 is added to the reaction batch as the crystallization accelerator. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein gealtertes Keimbildungsgel der Zusammensetzung (auf molarer Basis) SiO2/AlO- 2 ≥ 20, HO-/SiO2 = 0,05 bis 1,0, quaternäre Ammoniumverbindung/Si02 = 0,0 bis 2,0, vorzugsweise 0,01 bis 2,0, H20/Si02 = 10 bis 1000, verwendet.2. The method according to claim 1, characterized in that an aged nucleating gel of the composition (on molar basis) SiO 2 / AlO - 2 ≥ 20, HO - / SiO 2 = 0.05 to 1.0, quaternary ammonium compound / Si02 = 0.0 to 2.0, preferably 0.01 to 2.0, H 2 0 / Si0 2 = 10 to 1000 used. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die quaternäre Ammoniumverbindung ein Tetrapropyl-ammoniumsalz (TPA+), vorzugsweise das Bromid, oder Tetrapropylammoniumhydroxid (TPAOH) darstellt.3. The method according to claim 1 or 2, characterized in that the quaternary ammonium compound is a tetrapropyl ammonium salt (TPA + ), preferably the bromide, or tetrapropylammonium hydroxide (TPAOH). 4. Abwandlung des Verfahrens nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man statt der quaternären Ammoniumverbindung ein Amin, vorzugsweise ein Alkylendiamin, oder ein Gemisch aus einem Alkohol mit Ammoniak verwendet.4. modification of the method according to any one of claims 1 to 3, characterized in that instead of the quaternary ammonium compound, an amine, preferably an alkylene diamine, or a mixture of an alcohol with ammonia is used. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Keimbildungsgel bei atmosphärischem Druck im Bereich von 15 bis 100°C, vorzugsweise bei 20 bis 60°C, über 2 Stunden bis 100 Tage, vorzugsweise über 10 Stunden bis 50 Tage, gealtert worden ist.5. The method according to any one of claims 1 to 4, characterized in that the nucleation gel at atmospheric pressure in the range of 15 to 100 ° C, preferably at 20 to 60 ° C, for 2 hours to 100 days, preferably for 10 hours to 50 Days that has been aged. 6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man das gealterte Keimbildungsgel Reaktionsansätzen mit folgender Zusammensetzung (auf molarer Basis) zusetzt: SiO2/Al2O3 ≥ 5, HO-/SiO2 = 10-10 bis 1,0, quaternäre Ammoniumverbindung/Si02 = 0,01 bis 2,0, H20/Si02 = 0,7 bis 3000, Me/Si02 = 0,3 bis 3,0, wobei Me ein Alkali- oder Erdalkalimetall-Kation darstellt.6. The method according to any one of claims 1 to 4, characterized in that the aged nucleation gel reaction mixtures with the following composition (on a molar basis) is added: SiO 2 / Al 2 O 3 ≥ 5, HO - / SiO 2 = 10- 10 to 1.0, quaternary ammonium compound / Si02 = 0.01 to 2.0, H 2 0 / Si0 2 = 0.7 to 3000, Me / Si0 2 = 0.3 to 3.0, where Me is an alkali or alkaline earth metal -Cation represents. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man das gealterte Keimbildungsgel in Mengen von 4 bis 40 Gew.-%, vorzugsweise von 15 bis 25 Gew.-%, bezogen auf den Si02-Gehalt des fertigen Reaktionsansatzes, diesem zusetzt.7. The method according to any one of claims 1 to 6, characterized in that the aged nucleation gel in amounts of 4 to 40 wt .-%, preferably from 15 to 25 wt .-%, based on the Si0 2 content of the finished reaction mixture , adds to this. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man das gealterte Keimbildungsgel in einem Reaktionsansatz mit einer Temperatur von 40 bis 200°C anwendet.8. The method according to any one of claims 1 to 7, characterized in that the aged nucleation gel is used in a reaction mixture at a temperature of 40 to 200 ° C. 9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man dem Reaktionsansatz zusätzlich zu dem gealterten Keimbildungsgel ein Alkalifluorid, vorzugsweise Natriumfluorid, oder Ammoniumfluorid zusetzt, wobei das Molverhältnis F-/SiO2 = 0,4 bis 1,5 beträgt.9. The method according to any one of claims 1 to 8, characterized in that an alkali metal fluoride, preferably sodium fluoride, or ammonium fluoride is added to the reaction mixture in addition to the aged nucleation gel, the molar ratio F - / SiO 2 = 0.4 to 1.5 .
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CZ306416B6 (en) * 2015-09-03 2017-01-11 Unipetrol Výzkumně Vzdělávací Centrum, A. S. A method of producing hollow spherical particles of zeolite ZSM-5
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WO1998038131A1 (en) * 1997-02-27 1998-09-03 Süd-Chemie AG PROCESS FOR PRODUCING ZEOLITES WITH A HIGH Si/Al ATOMIC RATIO
WO2004020337A1 (en) * 2002-08-28 2004-03-11 Albemarle Netherlands B.V. Process for the preparation of doped pentasil-type zeolite using doped seeds
CZ299372B6 (en) * 2005-09-23 2008-07-09 Výzkumný ústav anorganické chemie, a. s. Process for producing ZSM-5 zeolite with controlled crystal size
CZ306416B6 (en) * 2015-09-03 2017-01-11 Unipetrol Výzkumně Vzdělávací Centrum, A. S. A method of producing hollow spherical particles of zeolite ZSM-5
CZ306852B6 (en) * 2016-03-15 2017-08-09 Unipetrol výzkumně vzdělávací centrum, a.s. A method of production of the ZSM-5 zeolite with a high proportion of pairs of aluminium atoms

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